Process for dyeing and printing
netrugen-containhng fibers



United States Patent 3,211,514 PROCESS FOR DYEING AND PRINTING NlTRUGEN-CONTAINHNG FIBERS Richard Casty, Kaiser-Angst, Alfred Berger and Walter Mosimann, Basel, and Heinz Abel, Reinach, Basel- Land, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a company of Switzerland No Drawing. Filed June 6, 1963, Ser. No. 285,886 Claims priority, application Switzerland, June 8, 1962, 6,954/62 11 Claims. (Cl. 8-93) It has been found that nitrogenous fibers can be dyed or printed in an advantageous manner by treating them with an aqueous preparation containing a wool dyestulf, as assistant a compound of the formula where R represents a hydrophobizing radical, X an acid water-solubilizing atom grouping and n:-l, 2, 3, 4 or 5 the ratio of water (which may contain additives) and assistant being selected so as to produce a two-phase system, whereupon the material so treated is subjected to a treatment with moist heat.

Nitrogenous fibers suitable for use in the present process are, for example, polyamide fibers from e-caprolactam, or from hexamethylenediamine and adipic acid or 1:12-aminoundecanoic acid; fibers from regenerated protein, silk or above all wool, if desired blended with other fibers such as acetate rayon, polyester, polyacrylonitrile or cellulose fibers (half-wool). Furthermore, there may also be mentioned non-textile nitrogenous materials of fibrous structure, such as leather and pelts.

As dyestulf there may be used any desired (preferably water-soluble) wool dyestuff suitable for dyeing wool by the exhaustion method; as relevant examples there may be mentioned:

Acid wool dyestuffs,

Chroming dyestuffs,

Complex metal compounds of dyestuffs containing sulfonic acid groups, in which 1 atomic proportion of copper or preferably of chromium is bound in complex union to 1 dyestuif molecule,

Complex chrominum or cobalt compounds that are free from sulfonic acid groups and from carboxyl groups not participating in the formation of the complex and in which 2 dyestuff molecules are bound in complex union to 1 atom of chromium or cobalt; particularly suitable are both water-soluble dyestufis (for example those which contain sulfonic acid amide groups and alkylsulfone groups) and complexes that are sparingly soluble to insoluble in water; when these latter compounds are to be used in the performance of the present process they must first be finely dispersed;

Complex chromium or cobalt compounds containing in the complex molecule a single :sulfonic acid group or carboxyl group not participating in the complex formation, in which 2 dyestuff molecules are bound in complex union to 1 atom of chromium or cobalt;

Complex chromium or cobalt compounds that contain in the complex molecule more than one solubilizing group (carboxyl and/or sulfonic acid groups) and in which 2 dyestulf molecules are bound in complex union to 1 atom of chrominum or cobalt;

Copper phthalocyanines containing sulfo-nic acid groups,

reactive dyestuffs, for example those with monochlorotriazine or dichlorotriazine residues, or dichlor-opyrimidine or trichloropyrimidine residues or ice groups, acrylami-de or a-halogentacrylamide groups or groupings convertible thereinto, and Sulfuric acid leuco esters of vat dyestuffs.

For dyeing blends of wool and other fibers there are used-apart from the Wool dyestuffs-the dyestuffs conventionally employed for the other type of fiber, for acetate rayon and polyester fibers, for example, dispersion dyestuffs; for cellulose fibers direct dyestulfs, and for polyacrylonitrile fibers dispersion dyestulfs or basic dyestuffs.

In addition to the dyestuff the preparation of the invention contains an assistant of the Formula 1. Among such assistants the compounds of the formula occupy a special position. In this formula 11 and X have the meaning defined above, and R represents an aliphatic, cycloaliphatic or aliphatic-aromatic radical, preferably a hydrocarbon radical with 10 to 22 carbon atoms. Such radicals are derived from alcohols, such as lauryl, tridecyl, oleyl, octadecyl or hydroabietyl alcohol; from carboxylic acids such as lauric acid or coconut oil fatty acid, or more especially from alkylphenols, such as octylphenol or nonylphenol.

The above-mentioned assistants are obtained when the said alcohols, acids or alkylphenols are reacted with 1 to 5, preferably 1 to 3, molecular proportions of ethylene oxide and then esterified with a halogencarboxylic or hydroxycarboxylic acid, for example chloracetic acid, or converted into an acid ester with the aid of an inorganic dicarboxylic acid such as maleic, ma-lonic or succinic acid, or preferably with a polybasic inorganic acid, such as orthophosphoric or above all sulfuric acid.

Particularly suitable for use in the present process are, accordingly, compounds of the formula where m is a whole number at least 7 and at the most 1 2, n is a Whole number from 1 to 5, preferably 1, 2 or 3, and X represents an acid water-solubilizing atomic grouping, preferably the radical of a polybasic inorganic acid. Alternatively, mixture of assistants of the Formulae 1 to 3 may be used, more especially those of which the on CH o radicals are not unitary so that the average value of n no longer represents a whole number, and may be for example about 1.5. It is of advantage to use instead of the acid ethers and esters their alkali metal, ammonium or amine salts in the manufacture of the aqueous preparations.

The assistants to be used in the present process form in water-Which, if necessary, may contain further additivesa two-phase system. The assistants to be used in the present process are hydrophilic surfa-ctive substances that form colloidal solutions and are capable of coacervation.

The term coacervation used in colloid chemistry indicates the demixing of a colloidal solution of a hydrophilic colloid with formation of two liquid phases, the phase containing more of the disperse phase being referred to as coacervate and the other as equilibrium liquid, The coacervate is characterized by the fact that a small amount of colloid contains a relatively large amount of water.

textile materials, also hydrotropic substances and the like. It is also possible to add an anti-foaming agent, such as a higher branched alcohol, for example 2-ethyl-hexano1 or 3:5 :S-trimethylhexanol and silicone oils, or to add substances that promote the dissolution of the compound forming the coacervate, for example lower alcohols, and do not have a disadvantageous effect on the formation of the two-phase system. Such additives may also be present in a suitable dye preparation from the start so that they need not be added to the aqueous preparation.

The amounts of the compounds used in the present process may vary W ithin rather wide limits and depend above all on the desired tinctorial strength of the dyeing; they may range from 0.4 to preferably from 0.5 to 7%, calculated on the total weight of the preparation.

When the dyestufl. is stirred into such a two-phase system, it is taken up largely to substantially completely by the phase containing the larger proportion of assistant and at least partially dissolved in it because this phase has a substantially greater solving power than water alone for the dyestuff, whereas the phase poorer in assistant generally contains less dyestuff. This two-phase systemwhich consists substantially of water, the assistant and the dyestuff and which contains as a rule not less than 10% of the phase richer in assistant (calculated on the total amount of preparation)can in general be homogenized without addition of an emulsifier by simple stirring to such an extent that statistically unitary preparations are obtained which have an adequate pot life and can be applied in a suitable manner to the fibrous material. By adding a thickening agent, for example British gum, the stability of the mixture, insofar as their homogeneity is concerned, can be enhanced.

The preparation to be used in the present process can be applied to the fibrous material in the known manner, advantageously continuously, for example by printing or, particularly advantageously, on a padder, which takes only very little time. Thus, for example, it suflices to introduce dry wool (combings or piecegoods) from above in between two contiguous horizontal pad rolls, the padding liquor being present only in the small interspace above the line of contact of the two rolls; this method is referred to in this connection as padding in the triangular interspace between the two rolls of a padder.

Alternatively, the material to be impregnated may be immersed and then the excess of impregnating liquor suctioned off or removed by centrifugation.

As a rule, dry material is inserted in the padding liquor. In special cases, for example when loose wool is to be impregnated immediately after leaving the last vat of the Leviathan washer, wetted and strongly expressed material may be so immersed.

The temperature of the liquor in the padder may vary within wide limits, for example from room temperature to 80 C., but it is preferably to perform the impregnation at room temperature. The phase richer in assistant, which contains the dyestuff, is not immediately fixed on the fiber but at first just remains adhering mechanically to it and can be completely washed off the surface of the wool fiber with cold water.

Instead of applying the impregnating liquor to the fibrous material on the padder, the material may be conducted over felt-covered transfer rolls revolving in the liquor. The liquor is absorbed by the felt and scraped on to the fibrous material in an easily adjusted amount.

Furthermore, the fibrous material can be conveyed through a fine spray or mist produced from the impregnating liquor, during which it is charged with the requisite amount of dye preparation. This step may be performed by any method and with the aid of any apparatus conventionally used in the textile industry for conditioning or moistening.

The impregnation of the fiber with the two-phase system is followed by fixation in moist heat. As a rule, the wet material is introduced into the steam or fixing chamber. The term saturated steam as used below designates steam slightly overheated by direct super heating or by admixture of hot air only to a degree such that the impregnated material can be raised to the desired steaming temperature without substantial condensation on the one hand and without partial drying on the other hand, whereupon the material is left to reside in an atmosphere of saturated steam. The moist heat treatment may be performed under the following conditions:

(a) Saturated steam under atmospheric pressure, either for 2 to 60 minutes, for example in a Mather Platt ager, or in other continuous agers, in a jigger box or on a pad roll machine, or for a longer period of time in a cottage steamer.

(b) Saturated steam having a higher temperature, for example for 3 minutes at 120 C. in a pressure steamer.

(0) Moist heat below 100 C., for example of 60 C., by impregnating the material on a padder, reeling it and wrapping it up airtight in a rubber blanket and keeping it so wrapped for 12 hours in a room maintained at C.

After this moist heat treatment it is absolutely necessary to clean the material to remove any excess dyestuff,

thickening agent and residual assistant; this cleaning con-' sists in general in a warm treatment in a bath to which a surface-active detergent and/or alkalies may be added. When dyeing Wool combings, for example, it is of advantage to perform these wet treatments in the back-wash.

When chroming dyestuffs are used, the dyeings obtained without addition of a chromium donor must then be treated in the known manner in a hot acid bath with bichromate to produce the dyestuff complex. When, however, it is desired to produce the chromium complex subsequently On the fiber likewise continuously, the predyed material must be continuously treated on the padder with a chromate solution, then once more steamed, thoroughly washed and, if necessary, acidified. Dyeings produced with sulfuric acid leuco esters of vat dyestuffs must be subjected to a conventional oxidation treatment.

The present process may be applied, however, not only to after-chroming but also to one-bath metallizations; for this purpose a suitable metal donor, for example an agent supplying chromium or cobalt, is added to the padding liquor, and the material to be dyed is then further treated as described above.

Suitable chromium or cobalt donors are, for example, salts of these metals. From among chromium donors there may be mentioned alkali metal bichromate and ammonium bichromate baltous acetate is mixed with an excess of aqueous am monia, whereupon a complex cobaltic compound is formed. The complex cobaltic compounds of the formula may likewise be used successfully.

The application of the process of the invention to slub printing results in better dyestuff exhaustion and allows as a rule the steaming time to be shortened. Whena slub printing machine is used the present process allows slubbings to be uniformly dyed continuously when the surface printing rollers are replaced by plain rollers.

For direct printing woolen piecegoods it has hitherto been absolutely necessary first to chlorinate the wool since otherwise the prints obtained would have been completely unsatisfactory. By working according to the present process very handsome prints can be achieved even on unchlorinated wool, more especially also with reactive dyestuffs. The printing paste used has a composition analogous to that of the padding liquors described above but it requires an addition of urea and/ or glycerine and, if desired, the consistency of the printing paste can be controlled by adding a larger amount of thickening agent. The prints are then further processed in the same way as dyeings.

When the afore-mentioned assistants are used it is possible to reduce the pH value of the dye preparations as desired, down to about 1, which may be of advantage in some applications. The shifting of the pH value into the acid range is preferably performed with acetic acid, or in some cases optionally with formic acid or sulfuric acid. Acid preparations require acid-resistant thickening agents, and in this connection, for example, etherified carubic acids from carob bean flour have proved suitable.

102 C., remain there for 1 hour and are then washed in a rinsing bath maintained at 40 C. The slubbings thus treated are of a black shade which is fast to washing.

The solution of the assistant of 44% strength is prepared in the following manner:

308 parts of the adduct from 1 mol of para-nonylphenol with 2 mols of ethylene oxide are mixed, while being stirred at 60 C., with 105 parts of urea within 15 minutes and then, within minutes, with 105 parts of amidosulfonic acid, and this mixture is boiled for 6 hours on a boiling water bath. It is then allowed to cool to 60 C., and 410 parts of water are added, to form a thickly liquid product which contains about 44% of the ammonium salt of the acid sulfuric acid ester of the adduct from 2 mols of ethylene oxide with 1 mol of para-nonylphenol.

Instead of the liquor prepared as described above there may be used other dye preparations, the procedure being otherwise identical. Similar results are obtained with the following liquors:

20 parts of the dyestuif of the formula The process is also very suitable for use on leather, pelts and furs. More especially, the assistants to be used according to this invention make it possible to dye at pH values that ensure a minimum of damage to the wool.

Finally, the present process may also be successfully applied to cleaning and at the same time dyeing greasy wool, for example wool in the yolk. This wool, which contains for instance natural wool fat, batching oil or spinning emulsions, can be treated according to the present process and cleaned following upon the steaming op eration in a bath containing ammonia or sodium carbonate and, if desired, also a detergent, instead of in a conventional rinsing bath. When dyeing was performed without addition of an acid, there is no need for adding ammonia or sodium carbonate.

Unless otherwise indicated, parts and percentages in the following examples are by weight.

Example 1 W001 slubbings are passed through a horizontal tworoller padder and impregnated in the triangular space between the rollers with a liquor at room temperature of the following composition:

50 parts of the dyestutf of the formula OH HO 60 parts of a solution of 44% strength of the ammonium salt of the acid sulfuric acid ester of the adduct from 2 mols of ethylene oxide with 1 mol of para-nonylphenol,

200 parts of an aqueous thickening of 5% strength of etherified carubic acids,

630 parts of water,

parts of chromium fluoride,

20 parts of formic acid of 85% strength.

The impregnated, expressed, wet slubbings are then introduced into a chamber filled with saturated steam of SiOaH The slubbings are dyed a red shade which is fast to washing.

35 parts of the dyestuff of the formula I I HzN a) 40 parts of a solution of 44% strength of the ammonium salt of the acid sulfuric acid ester of the adduct from 2 mols of ethylene oxide with 1 mol of para-nonylphenol,

200 parts of an aqueous thickening of 5% strength of etherified carubic acids,

705 parts of water, and

20 parts of acetic acid of 40% strength.

Steaming time: 20 minutes.

The slubbings are dyed a blue shade which is fast to washing.

30 parts of the chromium complex containing for every atom of chromium 1 molecule of the dyestuff of the formula 7 8 50 parts of a solution of 44% strength of the ammonium Steaming and rinsing are performed as in Example 1, salt of the acid sulfuric acid ester of the adduct from 2 but a steaming time of 20 minutes is adequate. The mols of ethylene oxide with 1 mol of para-nonylphenol, slubbings are dyed a red shade which is fast to washing. 200 parts of an aqueous thickening of strength of The 45%. solution of the assistant is prepared as deetheri fied carubic acids, 5 scribed in Example 1, except that 264 parts of the ad- 695 parts of water, and duct from 1 mol of para-nonylphenol with 1 mol of 25 parts of formic acid of 85% strength. ethylene oxide are esterified and then diluted with 320 Steaming time: 40 minutes. parts of water.

The slubbings are dyed a blue shade which is fast to Example3 g. Wool slubbings are impregnated on a two-roller padder as described in Example 1, but the liquor used has the parts of the dyestuff of the formula followmg composmon:

H0 15 parts of the dyestufi of the formula OH 3 15 N HOaS- N=NO l 1103 s 11(1) I\'TH-C (ll-NH;

C=N N N l N=N H Cl 50 parts of a solution of 44% strength of the ammonium 20 HO S SOaH C1 salt of the acid sulfuric acid ester of the adduct from 2 mols of ethylene oxide with 1 mol of para-nonylphenol, 10 parts of the dyestuif of the formula s oan ml) (In O H OOONH N=N s 1|\I/ I HO3S- NH-c C-NHOSO3H N 300 .parts of an aqueous thickening of 5% strength of i 90 parts of a 45% solution of a mixture of the ammonium etherified carubic acids, salts of the acid sulfuric acid esters of the adducts con- 627 parts of water, and taining per mol of para-tertiary octylphenol an aver- 3 parts of chloro-pentamine cobaltic chloride age of 1.5 mols of ethylene oxide,

200 parts of an aqueous thickening of 5% strength of [CO(NH3)5C1]C1Z etherified carubic acids, Steaming time: minutes. 655 Parts of Water and 40 30 arts of acetic acid of 407 stren th. A very fast, reddish brown dyeing of the cobalt comp 0 g plex of the above dyestufi is obtained Steaming and rinsing are performed as in Example 1, but the steaming time is only 30 minutes. The slubbings Example 2 are dyed a red shade which is fast to washing. Wool slubbings are impregnated on a two-roller padder Th6 Solution 0f the assistant is P p as as described in Example 1, but the padding liquoris comscribed in p fixcfiPt that 272 Parts Of a IniXtuTe posed as follows; of the adduct from 1 mol of para-tertiary octylphenol and an average of 1.5 mols of ethylene oxide are esterified and dissolved in 330 parts of water.

Instead of the padding liquor prepared as described 20 parts of the chromium complex containing for every atom of chromium one molecule each of the following dyestuffs: above there may be used other dye preparations, all

OH HO other conditions being identical. Similar results are obtained with the following liquors: HO3S N=NC v H ji 20 parts of the dyestufi" of the formula 3 1 NO; 6 and S0311 H0 /(|)-N-C SOzCH2CHz.O.S0zOH noas N=NC/ 1| G C=N CH: 50 parts of a solution of 44% strength of the ammonium C1 salt of the acid sulfuric acid ester of the adduct from 2 mols of ethylene oxide with 1 mol of para-nonylphenol,

300 parts of an aqueous thickening of 5% strength of etherified carubic acids,

620 parts of water, and 1 0 parts of acetic acid of 40% strength.

Steaming time: 30 minutes.

90 parts of a solution of 45% strength of the ammonium salt of the acid sulfuric acid ester of the adduct from 1 mol of ethylene oxide with 1 mol of paranonylphenol,

200 parts of an aqueous thickening of 5% strength of etherified carubic acids,

660 parts of water,and The slubbings are dyed a blue shade which fast to 30 parts of acetic acid of 40% strength. Z washing.

20 parts of the dyestulf of the formula N HQaS H NH(IJ CCl Ht 1. N=N- C HOzS- 503B 411 40 parts of a solution of 44% strength of the ammonium salt of the acid sulfuric acid ester of the adduct from 2 mols of ethylene oxide with 1 mol of para-nonylphenol,

200 parts of an aqueous thickening of strength of etherified carubic acids,

730 parts of water, and

parts of acetic acid of 40% strength.

Steaming time: 30 minutes.

The slubbings are dyed a blue-red shade which is fast to washing.

10 parts of the dyestuff of the formula SiOgH 40 pat-ts of a solution of 44% strength of the ammonium salt of the acid sulfuric acid ester of the adduct from 2 mols of ethylene oxide with 1 mol of pana-nonylphenol, 200 parts of an aqueous thickening of 5% strength of etherified icarubic acids, 740 parts of water, and 10 parts of acetic acid of 40% strength. Steaming time: minutes.

The slubbings are dyed a red shade which is fast to washing.

Similar results are obtained with analogous dyestuffs which,, however, contain a OH =OHCO group instead of the chloropropionyl group.

10 parts of the dyestuff of the formula 0 NH, II

50 parts of a solution of 44% strength of the ammonium salt of the acid sulfuric acid ester of the adduct from 2 mols of ethylene oxide with -1 mol of para-nonylphenol,

300 parts of an aqueous thickening of 5% strength of ethenfied carbuic acids,

630 parts of water, and

.10 par-ts of acetic acid of 40% strength.

Steaming time: 30 minutes.

The slubbings are dyed a blue shade which is fast to washing.

Similar results are obtained with analogous dyestuffs which, however, contain a CHz=COO group instead of the dibromopropionyl group.

1 0 Example 4 W001 .slub-bings are dyed on a two-roller padder as described in Example .1, but the padding liquor has the following composition:

10 parts of the cobalt complex containing for every atom of cobalt 1 molecule each of the following dyestuffs:

S C-20113 EN- 0 C-O-CHs and HO OH \C N I C SOzNH 30 parts of a solution of 50% strength of the ammonium salt of the acid phosphoric acid ester of the adduct from 2 mols of ethylene oxide with 1 mol of para-nonylphenol,

200 parts of an aqueous thickening of 5% strength of etherified caru-bic acids,

7130 parts of water, and

30 parts of acetic acid of 40% strength.

Steaming and rinsing are performed as in Example 1, except that the steaming time is 20 minutes. The slub- 'bings are dyed brown shades.

The 50% solution of the assistant is prepared in the following manner:

127.6 parts of urea phosphate are fused at 70 to C. with 311 parts of urea, within one hour heated to 155 10. and then kept for 30 minutes at 150 to 160 C. The blatch is allowed to cool to 1110 to C., the melt is mixed with 46.5 parts of the adduct from 2 mols of ethylene oxide with E1 mol of nonylphenol, and the whole is heated for 1 hour at to 'C., then allowed to cool to 110 C. The reaction product is dissolved in 30 parts of water and made up with water to .131 parts.

Example 5 Wool slubbings are impregnated on a two-roller padder las described in Example 1, but the liquor used has the following composition:

20 parts of the chromium complex containing per atom of chromium 2 molecules of the dyestuif of the formula I S 03 EN- O C-O-CHa 80 parts of a solution of 50% strength of the sodium salt of the acid maleic acid ester of the adduct from 2 mols of ethylene oxide with 1 mol of nonylphenol,

200 parts of an aqueous thickening of 5% strength of etherified carubic acids,

680 parts of water, and

20 parts of acetic acid of 40% strength.

Steaming and rinsing are performed as in Example 1, except that the steaming time is 20 minutes. The slubbings are dyed a grey shade which is fast to washing.

W001 slubbings are impregnated on a two-roller padder as described in Example 1, but the padding liquor used has the following composition:

20 parts of the cobalt complex containing per atom of cobalt 2 molecules of the dyestulf of the formula HO C1 s ozNHz Cl 80 parts of a solution of 50% strength of the ammonium salt of the acid sulfuric acid ester of the adduct from 5 mols of ethylene oxide with 1 mol of nonylphenol,

200 parts of an aqueous thickening of 5% strength of etherified carubic acids,

680 parts of water, and

20 parts of formic acid of 85% strength.

Steaming and rinsing are performed as in Example 1, but the steaming time is 20 minutes. The slubbings are dyed a claret shade which is fast to washing.

The 50% solution of the assistant is prepared as described in Example 1, except that 440 parts of the adduct from 5 mols of ethylene oxide with 1 mol of nonylphenol are esterified and dissolved in 420 parts of water.

Example 7 The assistants used in Examples 1 to 6 can be replaced with equal success by the following preparations:

(a) 95 parts of a solution of 42% strength of the ammonium salt of the acid sulfuric acid ester of the laurylsorbitan ester: The preparation follows the procedure in Example 1, except that 360 parts of a commercial laurylsorbitan ester are used instead of the ethylene oxide adduct andrthe reaction product is dissolved in 510 parts of water.

(b) 160 parts of a solution of 25% strength of the sodium salt of the acid sulfuric acid ester of the adduct from 1 mol of ethylene oxide with 1 mol of tridecyl alcohol, prepared in the following manner: In a stirring vessel 244 parts of the adduct from 1 mol of ethylene oxide with 1 mol of tridecyl alcohol are mixed within 1 hour dropwise with 122 parts of chlorosulfonic acid at 5-l0 C., and the batch is stirred on at this temperature for 1 hour. The hydrogen chloride formed is displaced with injected nitrogen. The thickly liquid sulfurized product is slowly stirred into 180 parts of sodium hydroxide solution of 30% strength mixed with 210 parts of ice. Finally, the batch is made up with water to 1380 parts.

(c) 80 parts of a solution of 50% strength of the ammonium salt of the acid sulfuric acid ester of coconut oil fatty acid diethyleneglycol ester, prepared thus: 220 parts of coconut oil fatty acid, 110 parts of diethyleneglycol and 1.1 parts of para-toluenesulfonic acid are heated for 6 hours at 110-115 C. under a pressure of 50 to 100mm. Hg in a stirring vessel equipped with a descending condenser, during which Water distills over. 312 parts of this esterification product are esterified with amidosulfonic acid as in Example 1 and then dissolved in 300 parts of water.

(d) 40 parts of the sodium salt of the glycolic acid ether of the adduct from 4 mols of ethylene oxide with 1 mol of para-tertiary octylphenol, prepared thus: 382 parts of the adduct from 4 mols of ethylene oxide with 1 mol of para-tertiary octylphenol are mixed for about 4 hours at 40 C. with 50 parts of powdered sodium hydroxide. After this time most of the sodium hydroxide has dissolved, and within 2 hours at 40 to 50 C. parts of sodium chloracetate are added portionwise. The batch is heated for 4 hours at 50 to 55 C., then mixed with benzene, the undissolved residue is suctioned off, and the benzene is finally distilled off under vacuum.

(e) 40 parts of the sodium salt of the acid sulfuric acid ester of the adduct from 4 mols of ethylene oxide with 1 mol of hydroabietyl alcohol, prepared thus: In a stirring vessel 745 parts of anhydrous pyridine are mixed at about 5 C. dropwise with 103 parts of chlorosulfonic acid, whereupon 373 parts of the adduct from 4 mols of ethylene oxide with 1 mol of hydroabietyl alcohol are slowly added at 40 C. The whole is heated for 2 to 3 hours at 40 to 45 C., cooled to 20 to 30 C., and neutralized with sodium hydroxide solution of 30% strength, then left to itself for 12 hours and the solid residue is filtered off, and the pyridine and water are removed under vacuum.

Example 8 W001 slubbings are impregnated on a two-roller padder as in Example 1, except that the padding liquor is composed as follows:

20 parts of the cobalt complex containing per atom of cobalt 2 molecules of the dyestuif of the formula 40 parts of a solution of 44% strength of the ammonium salt of the acid sulfuric acid ester of the adduct from 2 mols of ethylene oxide with 1 mol of nonylphenol,

910 parts of water, and

30 parts of acetic acid of 40% strength.

Steaming and rinsing are performed as in Example 1, but the steaming time is 20 minutes. The slubbings are dyed a red shade which is fast to washing.

Example 9 Slubbings are impregnated on a two-roller padder as described in Example 1, except that the padding liquor is compose as follows:

3 parts of the cobalt complex containing per atoms of cobalt one molecule each of the dyestuff of the formulae OH HO 1 l S 02 EN- a I O C- O C Hz and 13 14 20 parts of a solution of 44% strength of the ammonium HO salt of the acid sulfuric acid ester of the adduct from 2 C1 mols of ethylene oxide with 1 mol of nonylphenol, 200 parts of an aqueous thickening of strength of 5 I etherified carubic acids, C=N 757 parts of water, and Hogs l; 20 parts of acetic acid of 40% strength. 1

Steaming and rinsing are performed as in Example 1, 2 but the steaming time is 10 minutes. A light-brown dye- 10 ing is obtained 40 parts of a solution of 44% strength of the ammonium Example 10 salt of the acid sulfuric acid ester of the adduct from 2 mols of ethylene oxide with 1 mol of nonylphenol, f Plece good? unlf?rmly impregnated on a 200 parts of an aqueous thickening of 5% strength of padder wlth the following llquor. etherified Cambic acids, parts of the chromium complex containing per atom 720 parts of water, and

of chromium one molecule each of the dyestufis of the 20 parts of acetic acid of strength. formulae OH H0 The piece goods are then steamed in a continuous open 20 width steamer at about 103 C. and then washed in a HO blank rinsing bath heated at 40 C. The woollen piecea goods are dyed a brown shade which is fast to washing. Similar results are obtained with the following dyestufi containing per atom of metal 2 molecules of the dyestuffs N02 25 of the formulae shown below:

Dyestulf Metal Shade Cl HO COOH CN-C SO3H l 1- N=N-0 I 4 01- Yellow.

C=N CE.

2 HO3S N=NO\ Cr Orange.

I H3O N02 OH H 0 l 0 s HO3S N=NO I Cr Red. I H O Cl OH HO\ I 4 HO3S- -N=NG C0 Yellowish I brown.

CN I 3C 01 5 HO S- 8 Cr Navyblue.

OH HO 6 --N=N Cr Grey.

SO3H I Dyestufi Metal Shade OH OH 1 HO3S N=N@ e Reddish brown.

I I NO: H CCCH OH HzN 8 OzN-@N=N-@ Go Green.

I NO: 80311 Example 11 Example 13 Loose wool is immersed in the following liquor and then expressed:

45 parts of the chromium complex containing per atom of chromium 2 molecules of the dyestuff of the formula Steaming and rinsing are performed as in Example 1, except that the steaming time is minutes. The wool is dyed a black shade which is fast to washing.

Example 12 Woollen slubbings are printed on a slub printing machine with a printing paste of the following composition:

20 parts of the chromium complex containing per atom of chromium 1 molecule each of the dyestuifs of the formulae parts of a solution of 44% strength of the ammonium salt of the acid sulfuric acid ester of the adduct from 2,.

mols of ethylene oxide with 1 mol of nonylphenol,

200 parts of an aqueous thickening of 50% strength of,

British gum, 720 parts of water, and 20 parts of acetic acid of 40% strength.

Steaming and rinsing are performed as in Example 1, except that the steaming time is 20 minutes. The slubbings are printed a brown shade whichis fast to washing.

Woollen slubbings are impregnated on a two-roller padder as described in Example 1, but the liquor used has the following composition:

30 parts of the dyestuif of the formula -Q r I Steaming and rinsing are performed as in Example 1. The slubbings are dyed a red shade which is fast to washlng.

Instead of 10 parts each of potassium chromate, acetic acid of 40% strength and 690 parts of water there may be used 10 parts of potassium bichromate 3 part-s of acetic acid of 40% strength, and 697 parts of water.

Example 14 Crude, greasy sheeps wool, so-called wool in the yolk, is sprayed with a dye preparation and then expressed on a two-roller padder. The liquor used for spraying is composed as follows:

10 parts of the cobalt complex containing per atom of cobalt one molecule each of the dyestuif of the formulae SO OHa HN- 00-0-0113 and 50 parts of a solution of 50% strength of the ammonium salt of the acid phosphoric acid ester of the adduct from 2 mols of ethylene oxide with 1 mol of paranonylphenol,

200 parts of an aqueous thickening of strength of etherified carubic acids,

710 parts of water, and

30 parts of acetic acid of 40% strength.

The impregnated and expressed, wet greasy wool is then introduced in a cottage steamer and left there for 40' minutes at 102 C. in an atmosphere of steam. The steamed wool is then rinsed in a bath maintained at 50 C. which contains per 1000 parts of water 2 parts of sodium carbonate. In this bath the wool loses most of its fat content and of any other impurities. The wool is then washed clean in 2 to four further baths containing water heated at 50 C. The loose wool is thus washed and at the same time dyed a brown shade fast to washing in a single operation.

The 50% solution of the assistant is prepared as described in Example 4.

Example 15 A pure wool worsted molleton, which has not been washed after weaving, is impregnated on a two-roller padder with a liquor composed as follows:

20 parts of the chromium complex containing per atom of chromium 2 molecules of the dyestuff of the formula 18 with dye liquor and then expressed. The dye liquor is composed as follows: 30 parts of the chromium complex containing per atom of chromium 2 molecules of the dyestuif of the formula S 02 HN- a i O C- O- C H 80 parts of a solution of 44% strength of the ammonium salt of the acid sulfuric acid ester of the adduct from 2 mols of ethylene oxide with 1 mol of para-nonylphenol,

200 parts of an aqueous thickening of 5% strength of etherified carubic aids, and

690 parts of water.

Wool muslin from unchlorinated wool is printed on a slub printing machine to a cover of with the following printing paste:

15 parts of the dyestuff of the formula 80 parts of a solution of 50% strength of the sodium salt of the acid maleic acid ester of the adduct from 2 mols of ethylene oxide with 1 mol of para-nonylphenol,

200 parts of an aqueous thickening of 5% strength of etherified carubic acids, and

700 parts of water.

The material is steamed in a Mather-Platt continuous piece goods steamer for 15 minutes, then washed at 50 C. and then rinsed clean in water. The piece goods are dyed a grey shade and are thus freed from the spinning emulsion and dyed in a single operation.

The 50% solution of the assistant is prepared as described in Example 5.

Example 16 Unwashed loose wool (Wool in the yolk) is impregnated OCl1 HOJIS O 0Cu0 The printed material is then finished as described in Example 1 for slubbings. The resulting violet print is fast to washing.

Example 18 Half-wool piece goods, consisting of equal parts of wool and spun rayon, are impregnated on the padder and then expressed. The padding liquor has the following composition:

30 parts of the dyestufr of the formula 19 8 parts of the dyestuff of the formula o NH 3 NH- CH;

S'O H 40 parts of a solution of 44% strength of the ammonium salt of the acid sulfuric acid ester of the adduct from 2, mols of ethylene oxide with 1 mol of para-nonylphenol,

200 parts of an aqueous thickening of strength of etherified carubic acids,

parts of the reaction product of naphthalenesulfonic acids with formaldehyde,

692 parts of water, and

parts of acetic acid of 40% strength.

0 NH: NH 0 II I I ll SOaH HOaS 4 parts of the dyestuff of the formula H? (H) Ha t-0H;

HgN O NH? 50 parts of a solution of 44% strength of the ammonium salt of the acid sulfuric acid ester of the adduct from 2 mols of ethylene oxide with 1 mol of para-nonylphenol,

250 parts of an aqueous thickening of 5% strength of etherified carubic acids, 646 parts of water, and 20 parts of acetic acid of 40% strength.

The impregnated material is then immediately conveyed through a short infra-red heating zone, then reeled in a steam chamber having a wet-ball thermometer temperature of about 95 C., and left in that-chamber for 1 hour. After this storing the material is thoroughly washed with warm water in a washing machine and dried on a stenter. The fabric is dyed a blue shade which is fast to washing.

Example 20 Piece goods, consisting of equal parts of wool and polyacrylonitrile, are impregnated on a padder and then expressed. The padding liquor is composed thus:

10 parts of the dyestuif of the formula 5 parts of the dyestuif of the formula O' HOaS- 803K 40 parts of a solution of 44% strength of the ammonium salt of the acid sulfuric acid ester of the adduct from 2 mols of ethylene oxide with 1 mol of paranonylphenol,

200 parts of a 5% thickening of etherified carubic acids,

730 parts of water, and

15 parts of formic acid of 85% strength.

The material is then steamed at about 102 C. in a continuous open width steamer and washed in a blank rinsing bath maintained at 40 C. The wool is dyed a bluish red shade and the polyacrylonitrile fiber a blue shade.

Example 21 Carpeting, having a jute backing and a pile from crimped polyamide yarn, is impregnated on a pad roll machine and expressed. The impregnating liquor is composed thus:

40 parts of the chromium complex containing per atom of chromium 1 molecule of the dyestuif of the formula H0 HO S OH N=NO 1 H C=N 3 Cl 40 parts of a solution of 44% strength of the ammonium salt of the acid sulfuric acid ester of the adduct from 2 mols of ethylene oxide with 1 mol of para-nonylphenol,

200 parts of an aqueous thickening of 5% strength of etherified carubic acids,

690 parts of water, and

30 parts of formic acid of 85% strength.

Immediately following, the impregnated material is conveyed through a short infra-red heating zone, then reeled in a steam chamber having a wet-ball thermometer temperature of about 92 C. and left there for 90 minutes. After having been stored, the material is Washed in a rinsing bath maintained at 40 C. The polyamide fiber is dyed a red shade which is fast to washing.

Example 22 Suede leather manufactured by a conventional chrome tanning process is kept immersed, until it is dyed right through, in a dyebath of the following composition:

30 parts of the dyestuff of the formula Ha? SIO 3 (I? IITH CH3 H30 1 l I NH CH2 40 parts of a solution of 44% strength of the ammonium salt of the acid sulfuric acid ester of the adduct from 2 mols of ethylene oxide with 1 mol of para-nonylphenol,

21 100 parts of an aqueous thickening of strength of etherified carubic acids, 820 parts of water, and parts of acetic acid of 80% strength.

The leather treated in this manner is then expressed to a residue liquor content of 100%, wrapped in a plastic film and stored for 4 to 10 hours in a heating cabinet maintained at 60 C. Any unfixed share of dyestuff is then washed out in a neutral to alkaline bath. The goods worked in this manner may be treated in an acetic acid or formic acid bath. The leather is dyed a blue shade which is fast to rubbing.

Similar results can be produced on other leathers obtained by a conventional chrome tanning method, for example glove or clothing leathers or splits.

Example 23 A sheeps wool skin is dyed by being brushed with a dye liquor of the following composition (the increase in weight being 200%):

40 parts of the dyestuff of the formula 40 parts of a solution of 44% strength of the ammonium salt of the acid sulfuric acid ester of the adduct from 2 mols of ethylene oxide with 1 mol of para-nonylphenol,

100 parts of an aqueous thickening of 5% strength of etherified carubic acids,

810 parts of water, and

10 parts of acetic acid of 80% strength.

The skin treated in this manner is then wrapped up in a plastic film and stored for 6 to 10 hours in a heat cabinet at 60 C. Any unfixed share of dyestuff is then washed out in a neutral to alkaline bath. The goods worked in this manner may be treated in an acetic acid or formic acid bath. The skin is dyed a red shade which is fast to rubbing.

What is claimed is:

1. Method for coloring wool in a continuous Way, wherein the wool is impregnated with an aqueous preparation of acid to neutral reaction comprising a wool dyestutf and as assistant a compound of the formula wherein R stands for a member selected from the group consisting of an aliphatic, cycloaliphatic and aliphaticaromatic hydrocarbon radical, X represents an acid watersolubilizing atomic grouping and n a whole number of at most 5, the ratio between water and the assistant being selected so that a two-phase system is formed and the material treated in this manner is then subjected to the action of steam.

2. Method for coloring wool in a continuous way, wherein the wool is impregnated with an aqueous preparation of acid to neutral reaction comprising a wool dyestufi and as assistant a compound of the formula wherein R stands for an aliphatic hydrocarbon radical containing 10 to 22 carbon atoms, X represents an acid water-solubilizing atomic grouping and n. a whole number of at most 5, the ratio between Water and the assistant being selected so that a two-phase system is formed and the material treated in this manner is then subjected to the action of steam.

3. Method for coloring wool in a continuous way, wherein the Wool is impregnated with an aqueous prepara- 22 tion of acid to neutral reaction comprising a wool dyestuff and as assistant a compound of the formula wherein R stands for a cycloaliphatic hydrocarbon radical containing 10 to 22 carbon atoms, X represents an acid water-solubilizing atomic grouping and n a whole number of at most 5, the ratio between water and the assistant being selected so that a two-phase system is formed and the material treated in this manner is then subjected to the action of steam.

4. Method for coloring wool in a continuous way, wherein the wool is impregnated with an aqueous preparation of acid to neutral reaction comprising a wool dyestutf and as assistant a compound of the formula wherein R stands for an aliphatic aromatic hydrocarbon radical containing 1.0 to 22 carbon atoms, X represents an acid water-solubilizing atomic grouping and n a whole number of at most 5, the ratio between water and the assistant being selected so that a two-phase system is formed and the material treated in this manner is then subjected to the action of steam.

5. Method for coloring wool in a continuous way, wherein the wool is impregnated with an aqueous preparation of acid to neutral reaction comprising a wool dyestutf and as assistant the sodium salt of the acid sulfuric acid ester of the adduct from 1 mol of ethylene oxide with 1 mol of tridecyl alcohol, the ratio between water and the assistant being selected so that a two-phase system is formed and the material treated in this manner is then subjected to the action of steam.

6. Method for coloring wool in a continuous way, wherein the wool is impregnated with an aqueous preparation of acid to neutral reaction comprising a wool dyestutr' and as assistant the sodium salt of the acid sulfuric acid ester of the adduct of 4 mols of ethylene oxide with 1 mol of hydroabietyl alcohol, the ratio between water and the assistant being selected to that a two-phase system is formed and the material treated in this manner is then subjected to the action of steam.

7. Method for coloring wool in a continuous way, wherein the wool is impregnated with an aqueous preparation of acid to neutral reaction comprising a wool dyestuff and as assistant a compound of the formula wherein m is a whole number of at least 7, X represents an acid water-solubi-lizing atomic grouping and n a whole number of at most 5, the ratio between water and the as sistant being selected so that a two-phase system is formed and the material treated in this manner is then subjected to the action of steam.

8; Method for coloring wool in a continuous Way, wherein the wool is impregnated with an aqueous preparation of acid to neutral reaction comprising a wool dyestuff and as assistant a compound of the formula wherein m is a whole number of at least 7 and at the most 12 and n is a number of at most 5, the ratio between water and the assistant being selected so that a two-phase system is formed and the material treated in this manner is then subjected to the action of steam.

9. Method for coloring wool in a continuous way, wherein the wool is impregnated with an aqueous preparation of acid to neutral reaction comprising a wool dyestutf and as assistant the ammonium salt of the acid sulfuric acid ester of the adduct from 2 mols of ethylene oxide with 1 mol of p-tertiarynonylphenol, the ratio between water and the assistant being selected so that a 23" two-phase system is formed and the material treated in this manner is then subjected to the action of steam.

10. Method for coloring wool in a continuous Way, wherein the wool is impregnated with an aqueous preparation of acid to neutral reaction comprising a wool dyestuff and as assistant a mixture of the ammonium salts of the acid sulfuric acid esters of the adducts containing per mol of p-tertiary octyl-phenol an average of 1.5 mols of ethylene oxide, the ratio between water and the assistant being selected so that a two-phase system is formed and the material treated in this manner is then subjected to the action of steam.

11. Method for coloring nitrogenous fibers, wherein the wool is impregnated with an aqueous preparation of acid to neutral reaction comprising a wool dyestufi and as assistant a compound of the formula aromatic hydrocarbon radical, X represents an acid watersolubilizing atomic grouping and n a whole number of at most 5, the ratio between water and the assistant being selected so that a two phase system is formed and the material treated in this manner is then subjected to the action of steam.

References Cited by the Examiner UNITED STATES PATENTS 8/37 Kritchevsky 887 X 10/ 62 Radley et a1. 893

OTHER REFERENCES 9 page 107.

NORMAN G. TORCHIN, Primary Examiner. 

1. METHOD FOR COLORING WOOL IN A CONTINUOUS WAY, WHEREIN THE WOOL IS IMPREGNATED WITH AN AQUEOUS PREPARATION OF ACID TO NEUTRAL REACTION COMPRISING A WOOL DYESTUFF AND AS ASSISTANT A COMPOUND OF THE FORMULA 